Treatment of yarns and fabrics



Patented June 11, 19 29.

GEORGE HOLLAND ELLIS, OF SPONDON,

NEAR DERBY, ENGLAND, ASSIGNOR TO CELANESE CORPORATION OF AMERICA, A CORPORATION OF DELAWARE.

TREATMENT OF YARNS AND FABRICS.

No Drawing. Application filed January 22, 1926, Serial No. 83,138, and in Great Britain September 7, 1925.

This invention relates to the dyeing or colouring of yarns, fabrics or other materials or articles.

The invention'has for its principal object to provide a new or improved process or processes for the dyeing. printing or stencilling (all hereinafter in the claiming clauses included in the term d ycing) of fabrics,fibrcsor other materials with colouring matters or organic compounds by vatting, that is to say by or with the aid of vatting.

It is well known that the application of coloring matters to many textile products by Vatting methods has hitherto been difficult or impossible, owing to the deleterious action upon the fibres of the strong alkalis, particularly caustic soda and caustic potash, necessary for use for the successful practice with these methods. Coloring matters which are applied by such methods are generally included in the term vat dyestuffs, which term includes a considerable variety of typical chemical classes and the sulphide or sulphur dyestuffs, which include a wide variety of sulphurized organic compounds. Commercial fibres in connection with which the application of such colours by vatting methods showed this difficulty are chiefly the animal fibres such as wool and silk, and substances of animal origin such as hair, fur, leather and the like, cellulose acetate, and, to a less extent, artificial silks or artificial fibres of the cellulosic type. The deleterious action of caustic alkalis, such as hydroxides of soda and pot-ash, in aqeoussolution, in causing a degradation of these animal fibres, cellulose acetate or other artificial fibres is well known; in the case of the animal fibres or. substances there results a loss in tensile strength, contraction, felting of the, fibres and other physical results of partial degradation; in the case of cellulose acetate there is progressive loss in weight with some loss of lustre and strength, and change in dyeing properties; in the case of the artificial fibres of the cellulosic type, the degradation is less marked but may show less of lustre and strength. Y According to the present invention I pre Vent or ameliorate the aforesaid (lifliculties in the application of such. coloring matters by vatting methods, by using in partial or total substitution of the strong alkalis before mentioned, compounds which have very much less tendency to attack the substances or fibres before referred to, but which nevertheless render possible the successful application of the dyestuffs.

The substances I employ in partial or total substitution of the strong alkalis before mentioned are salts of hydroxy or poly-hydroxy, or of simple. ring-substituted derivatives of hydroxy or polyhydroxy compounds of the homocyclic or hetcrocyclic organic series, such as the benzene, naphthalene, anthracene, or pyrazol series and the like. Preferably I employ alkali metal or ammonium salts, though I do not limit myself in this respect, as I may employ, though less advantageously, salts of other metals, such for example as water-soluble earth alkali metal salts or other salts of the aforesaid hydroxy or polyhydroxy bodies, or their derivatives.

It is of course understood that I may employ any of such substances, or mixtures containing two or more of such substances.

The following are some examples of compounds which I may employ for the purpose of the present invention, it being understood that they are in no way limitative:

Sodium phenate; potassium phenate; sodium cresolate; potassium cresolate; sodium xylenolate; potassium xylenolate; sodium catecholate; potassium catecholate; sodlum resorcinate; potassium resorcinate; sodium guaiaeolate; potassium guaiacolate; sodium quinolate; potassium quinolate; sodium betanaphtholate; potassium betanaphtholate; sodium alphanaphtholate; potassium alphanaphtholate; sodium para'chlorphenate; d1- sodiumleucoanthraquinonate.

In carrying out the invention I may employ any coloring matters or orgamc compounds capable of being applied by vattlng methods. Such coloring matters or compounds may for example belong to the generic series:

Benzoquinone; Naphthoquinone; anthraquinone (including dibenzanthrone and isodibenzanthrones, anthraquinone azines and hydroazines, flavanthrone, amino anthraquinones or aminohydroxy anthraquinones or substituted derivatives thereof containing one or more alkylaminoor arylamino groups or both alkylamino and arylamino groups, acylamino or substituted acylamino anthraquinones, anthraquinonyl amines, anthrapyridones, anthraquinoneacridones and naphthaeri'dones, anthraquinone thioxanthones) phcnanthraquinone; aceanthrenequlnone; naphthanthraquinone indophenol carbazol indigoid (including naphthindigoid, acenaphthene indigoid, anthracene indigoid,

isoindigoid); thiocarbazol, thio-indigoid or.

other sulphurized derivatives of the above mentioned classes usually comprised within the term vat dyestuffsand the sulphurized compounds usually comprised within the term sulphur or sulphide dyestuffs.

In the ordinary known methods of application of such substances as before referred to, as vat dyestuffs, the coloring matter is eniployed with the alkali hydroxide in conjunction with the reducing agents commonly employed in vat dyeing, such for instance as hydrosulphites. In the case of sulphur or sulphide dyestufi's it is usual to employ sulphites in conjunction with the hydrosulphites or other reducing agents and alkali hydroxide.

In performing'the present invention the alkali hydroxide may be partially or entirely substituted or replaced by one or moreof the alkali metal or ammonium salts, or other water-soluble salts of hydroxy, polyhydroxy, or simple ring substituted derivatives of hydroxy or polyhydroxy, compounds of the homocyclic or heterocyclic organic series such for instance as those before mentioned, at any stage as desired, either in preparing the dyestulf in the reduced form in solution, or in the dyebath (or printing etc. preparation) itself, or both. The salts may be used as such, or they may be produced in solution by first carrying out the preparation of the coloring matter or dyebath with free alkali hydroxide, afterwards adding the free hydroxy body in suitably adjusted quantities. Similarly in the case of printing and like pastes or preparations the salts may be used as such or may be produced analogously with in the paste or preparation.

It is well known that attempts have been .made to reduce the causticity of the dyebaths or solutions in the application of vat and sulphur colors by vatting methods, by the use of acids such as benzoic, tartaric, acetic lactic and the like. Such substances, however, since they are usually more strongly acid or saltforming thamthe leuco dyestufi' molecule it-- self, frequently cause precipitation which is possible to animal fibres and cellulose acetate,

and other fibres which are deleteriously affected by strong alkalis.

Besides enabling a more successful application of the antlnaquinone, indigoid and other vat dyestufis and sulphide dy stuffs individually to wool real silk, and other substances of animal origin and to cellulose acetate and other artificial fibres, the invention enables valuable applications to be made to mixc'dgoods containing such fibres, and to mixed goods containing such fibres and vegetable fibres. The dyeing, printing or stencilling of such mixed goods may be affected in solid or varying shades according to the relative affinities of the components towards the dyestuffs employed, and may be performed with or without previous or subsequent application of any other suitable dyestulfs to the goods. Thus for example mixtures of cotton or other vegetable fibres with wool, silk or other animal fibres, may be treated with vat or sulphide dyestuffs by the process of the present invention without causing such degradation to the animal fibres as was formerly experienced when using the strong alkali hydroxide methods; and uniform or differential efl'ects may be obtained on such mixed goods with a suitable selection of the individual coloring matters and by the exercise of suitable practical control of temperature and other conditions of dyeing. In like manner mixtures of cellulosic artificial fibres with animal fibres may be dyed, printed or stencilled while preserving the original qualities of both components.

Similarly with mixtures containing cellulose acetate yarns, filaments or fibres, a wide variety of effectsmay be obtained according to the relative alfinities of the components of the mixed goods for the selected colors. Thus mixed goods containing cellulose acetate and cotton or other cellulosic fibres or wool or other animal fibres may be treated to yield uniform or varying effects.

The present invention may be performed in presense or absence of protective colloids. In the case of sulphide colors, sulphites may be used in conjunction with the hydrosulphites used for forming the leuco compound.

The following examples are given by way of illustration of the invention, it being understood that they are in no way limitative.

Example .1.

dyed for 30-45 minutes, during which time the temperature is raised to 50 C. It is dyed for a further 4 hr. at 50 C. then lifted, rinsed, and finished accordingto the method common in the art when dealing with such goods.

Example 12.

To dye a reddislrviolet shade on 100 kilos of acetyl cellulose yarn in the form of hanks, take 2 kilos of 44'-dimethyl-5-5 dichlor 7-7 dimethoxy 2.2 bisthionaphthene indigo (known as thio indigo violet 2B powder color index No. 1219), paste with a small quantity of an alkali salt ofa sulphated oil such as sulphoricinoleie acid (e. Turkey red oil, solubleoil, Turkonoil, etc.) to aid wetting out, and gradually add 7 litres of disodium resorcinate 19% solution. To this now add 15 litres of soft water, heat up to 40 C. and dredge in 6 kilos of sodium hydrosulphite powder. Stir very gently for 20 minutes and add this stock vat to a dyebath of 2500 litres soft water at 40 C. set with 2 litres of disodium resorcinate 5 solution 19% and 400 grms. of sodium h-ydrosulphite powder. Enter the previously scoured yarn and dye from to'% hr. at 40 (1, lift, squeeze, rinse and oxidize in a bath containing 1 gram per lltre soap and 1 gram per litre sodium perborate at 45 0. Finally rinse off and finish as may be required.

Example 3.

of the anthraquinone vat color known as indanthrene red violet RRK powder color in dex No. 1161 are pasted with a small quantity of an.alkalisalt of a sulphated oil such as sulphorici'noleic acid (e. g. Turkey red oil,

soluble oil, Turkon oil, etc.) to aid wetting out, andl litre of caustic soda solution 10%,

and the resulting liquor is sieved into the aforementioned dyebath. 500 grams of sodium hydrosulphite are then dredged in and the bath gently raked at intervals during 20 minutes when vatting will be complete. 5.6

. kilos of phenol are dissolved in a sufiiciency of soft water and the solution slowly poured with stirring into the dyebath. After a thorough mixing the bath is ready for the dyeing operation which is carried out according to the procedure normally followed in the art.

Ewample 4..

To dye a dull blue shade on 100 kilos of woolen yarn in the form of hanks, take 2 kilos of'the sulphide dyestulf known as thio- 1101 direct blue S, 20 litres ofpotassium phenate solution 34.5% and paste these together, adding 40 litres of soft water to the color paste; heat up to 30 C. and stir in gently 1 kilo of sodium hydrosulphite powder. Allow to stand for a short time until vatting is complete and add this stock vat to a dyebath containing 2400 litres of soft water to which has previously been added 2 litres potassium phenate 34.5% solution and 400 grams sodium hydrosulphite and 20 kilos of common salt. Enter the previously scoured woollen yarn and gradually raise the temperature of the bath to C. during hr. Dye at this temperature for a further to 5!; hour, lift, squeeze, oxidize and rinse according to the usual practice in the art for this type of goods.

E example 5. I

'lo dye a deep blue shade on 100 kilos of powder and allow to stand. After 15 minutes, when vatting is complete, pour this solution of the reduced dyestutf into 4000 litres of soft water and add 4 litres sodium-orthocresolate solution 32.5%, 600 grains sodium hydrosulphite and 20 kilos of common salt in the form of a concentrated solution. Enter the previously degummed silk into the cold dyebath, raise the temperature to C. in hour, and dye at 80 C. for a further hour. Lift out, squeeze, rinse off and oxidize by allowing to hang in the air. Finally soap and finish as may be desired.

E example 6.

To dye an old rose shade on 100 kilos of real silk yarn in the form of hanks, prepare a dyebath containing 2500 litres of soft water with litres sodium parachlorphenate solution 37.5% the temperature of the bath being 20 C. Sieve in 15 kilos of the anthraquinone dyestuif known as indanthrene pink B paste and then dredge in 7 kilos of sodium hydrosulphite powder. Rake the bath gently, and when vatting is complete, enter the previously boiled-off silk yarn; work for hour, during which time the temperature is raised in the art.

to C. Lift, squeeze and oxidize, finally finishing according to the method common Example 7.

To dye a bright green on the cotton and a lemon yellow on the acetyl cellulose in 50 kilos of an acetyl cellulose and cotton fabric containing these two fibres in equal proportions, a stock vat is first prepared as follows 2- 2 kilos of 3.3 dichlor.N.dihydro 1.2:1'2' anthraquinoneazine (known as duranthrene blue GCD color index No. 1113) are pasted with a small amount of the alkali salt of the sulpho acid of a higher fatty acid, for instance sulphoricinoleic acid (e. g. soluble oils, Turkey red oil, Turkon oil, etc.) to aid wetting out, and 2 litres of disodium resorcinate solution 19%. The paste is then poured into a bath containing 50 litres of soft water into which has been stirred 5 kilos of the brominated indigoid vat dyestufi known as Ciba yellow G color index No. 1196 paste and98 litres of disodium resorcinate solution 19%. This bath is heated to 40 C. and 4 kilos of sodium hydrosulphite powder dredged in; and bath is well raked and reduction is complete at the end of 15 minutes. The dyebath 1s prepared in a suitable machine containing 1000 litres of soft water, raised to a temperature of 40 C. from which the oxygen has been removed by the addition of 3 litres of disodium resorcinate solution 19% and 250 grams of sodium hydrosulphite powder: the stock vat prepared as above is added to the machine, the-fabric entered and dyed for to hour at a temperature of 50 (1.; it is then removed and treated in the manner usual in the art when dyeing such goods.-

Ewample 8.

To dye 25 kilos of fabric composed of cotton and acetyl cellulose yarns in equal proportions, so that a green shade is obtained on the cotton and a bluish red shade on the acetyl cellulose, the cotton is first dyed in a suitable machine, the dyebath being prepared as follows 600 litres of soft water are heated to 30 C. and 37.5 litres of sodium paracresolate 32.5% solution are added. Into this is sieved 2.5 kilos of the anthraquinonoid "at dyestufi ob.- tained by oxidation of dibenzant-hrone and subsequent treatment with methyl sulphate, and known as Caledon jade green color index No. 1101 paste. .650 grams of sodium hydrosul hite powder are now dredged in and the bat raked over gently until reduction is complete. The previously scoured ofl' material is entered and worked for 20 minutes during which time the temperature is raised to 50 C; dyeing being then continued for a further 15 minutes at this-temperature, when the goods are removed from the bath, squeezed, oxidized, rinsed and the full shade on the cotton is developed in a bath containing 1 gram per-litre of olive oil soap and 1 I litres of sodium sulphoricinolcate (50%); I

the mixture is heated under an open steam pipe and then diluted with water and further boiled. The liquor is then filtered into a dyebath containing 600 litres of cold soft water in which is dissolved with advantage suflicient sodium sulphoricinoleate (50%) to bring the final concentration of the bath to 3 cubic centimetres of the ricinoleate (50%) per litre. The goods are then entered and dyeing carried out inthe customary manner, the temperature being raised to C.- to aid exhaustion. When the desired depth has been obtained the goods are lifted, rinsed, dried, and otherwise treated or finished as desired.

E'vmmzple 9.

toluylenediamine and sulphur and then treatinto a paste with water and this paste added to the bath, after which 1 kilo of sodium qhydrosulphite powder is dredged in and the bath gently stirred for 15 minutes. The goods are now entered, worked at a temperature of 40 C. for 15 minutes, and the term perature then raised to 75 C. in 15 minutes, at which temperature the goods are worked for a further 15 minutes. They are then lifted squeezed and oxidized, and rinsed, and after full development of the shade on the cotton, the acetyl cellulose component is dyed a bright violet according to the 300 grams of dimethyl-para-aminophcnyl-1.4- naphthoquinone-monoimide (33% paste) and 100 grams of 2.4-dinitrobenzene-azo-dicthylaniline (25% paste) are well mixed with 1875 cubic centimetres'of sodium sulphoricinoleate (50%) which has previously been heated to 100 C. After about 10 minutes the mass is diluted with boiling water and the whole is filtered into the dye machine containing 600 litres of cold soft water. Dyeing is carried out in the customary manner, the temperature being raised to about 75 C. to aid exhaustion. The goods when dyed as I ing with sodium hydroxide are then made as desired.

Ewample 10.

To dye a bright green shade on the wool and a bluish red shade on the acetyl cellulose yarns contained in 20 kilos of a fabriccomposed of equal proportions of these two fibres, the wool is first dyed according to Example 3 above, using 1 kilos of the anthraquinone vat dyestuff known as Caledon jade green color index No. 1101 paste in place of indanthrenered violet RRK powder,.the procedure being precisely similar."x' 'lhe acetyl cellulose'c'omponent is -.thcn' colored according to the method given in Example 8, but using 2.4-dinitrobenzene-l azo-dimethylaniline instead of 2.4-dinitrobenzene-l-azo-diethylaniline therein cited, the procedure being otherwise precisely similar.

Example 11.

20 kilos of a fabric made up from equal weights of real silk and acetyl cellulose yarns, are dyed to give a yellow shade on the silk and to give a green shade on the acetyl cellulose according to the following method Paste 400 grams of the dyestulf (known as Cibanone orange R color index No. 1169) yielded by hypochlorite oxidation of the product resulting from the sulphurization of 2-methylanthraquinone (or its chlor derivatives,) with 48 litres of sodium phenate solution 30% warmed to 60 C. and add l kilos of sodium hydrosulphite powder. When vatted, pour into a suitable machine containing (500 litres of soft water previously set with 600 ccs. of sodium phenate solution of 30% and 100 grams of sodium hydrosulphite.

Enter the previously prepared fabric, Work for one hour, lift and treat as is usual when dyeing vat colors on such fabrics. Finallypull up the acetyl cellulose component to-a green shade according to the method given in Example 9, using a mixture in any suitable proportions of 1-methylan1ino-4-paratolylaminoanthraquinone and 4-chlor-2-nitro-4- ethoxy-diphenylamine in place of the dyestuffs therein cited. The procedure is otherwise precisely similar.

- Ewample 2 kilos of 2(5-bromoindole) -2 thionaph thene indigo (known as Ciba grey B color index No. 1220) are pasted with 30 kilos of dipotassium resorcinate solution 23% and the temperature raised to 60 C. 8 kilos of sodium hydrosulphite are now sieved in and the liq-.

uor gently stirred. After 15 minutes, when reduction is complete, this stock vat is poured into 5000 litres of soft water 50 C. previously set with 5 litresof dipotassium resorcinate solution 23%, and 800 grams of sodium hydrosulphite powder. The previously scoured off yarn is entered into the well stirred dye bath, and worked for 1 hour at 55 C. It is then lifted, squeezed, rinsed and oxidized by treatment in a bath at C. containing 1 gram per litre soap and 1 gram per litre sodium perborate. The yarn is finally finished as required. The silk will have acquired a pale blue Violet shade, while the acetyl cellulose has a deep and redder violet tone.

Emampl e 15.

To dye20 kilos of a fabric composedof a mixture ofequal weights of cotton, wool and acetyl cellulose yarns, so that the cotton is 600 grams of the sulphide dyestulf known as thionone dark brown MD are vatted according to the method given in Example 9 hereof, replacing the thionone yellow 2R by this color, and the dyeing of the cotton is carried out as there directed. The acetyl cellulose component is now dyed a bright red by dispersing 66 grams of QA-dinitro-benzeneazo-p-xylidine in 650 grams of sodium sulphoricinoleate (50%), heating, diluting with water and boiling in a manner similar to that given in Example 8. This dispersion is then added to a fresh dyebath containing soft water in the ratio of about 30:1 on the weight of the goods. usual manner and the goods are removed and afterwards rinsed as desired. After lifting and rinsing off the goods from this process the wool is then dyed up to a bright blue shade from a bathcontaining the sodium salt of 4.8 diamino-1-5-dihydroxyanthraquinone- 2-6 disulphonic acid, and Glaubers salt, the

free color acid being liberated by addition of 1 acids, organic or mlneral, 1n known manner or compounds hereinbefore referred to which are capable of application in sulphide solutions may be applied to the dyeing, printing. or stenciling of the goods by the so-called sulphide method, i. e. in sulphide solutions, instead of being ,reduced by hydrosulphites or the like; and in this method also I replace partially-or entirely by the alkali metal, ammonium or other salts hereinbefore referred to, thestrong alkali ordinarily employed in such processes. Coloring matters or. compounds Which may be applied by this method are'generally termed sulphur, sulphide or sulphur vat dyestuffs or coloring mat- ,ters. Preferably in employing this modification of the invention I employ alkali hy- Dyeing is then done in thedrogen sulphides in' place of the alkali sulphides usually employed in sulphide dyeing.

According to another part of my invention the alkali metal, ammonium or other salts hereinbefore referred to may be applied wholly or partly in place of strong alkalis in baths or solutions for desizing thread, yarns and fabrics liable to be detrimentally affected by strong alkali, especially yarns, threads and fabrics consisting of or comprising cellulose acetate.

The term materials used in the claims is intended to cover any of the materials previously mentioned whether used singly or in combination. It is to be understood that the term materials comprising artificial fibres derived from cellulose used hereinafter in the claims includes materials comprising artificial ,silks or other artificial fibres of organic substitution derivatives of cellulose, such as cellulose acetate, as Well as materials comprising artificial silks or other artificial fibres of the cellulosietype. Furthermore the phrase methods normally using strong alkali in the claims is to be understood to include both the vatting. and the sulphide methods referred to above. v e

What I claim and desire to secure by Letters Patent is 1. In a process of dyeing materials by methods normally using strong alkali, the step of replacing, at least partially, the strorig alkali by a soluble salt of a hydroxy compound of the cyclic organic series.

2. In a process of dyeing materials comprising artificial fibres derived from cellulose, by methods normally using strong alkali, the step of replacing, at least partially, the strong alkali by a soluble salt of a hydroxy compound of the cyclic organic series.

3. In a process of dyeing materials by a vatting method,- the ste of replacing, at least partially, the strong a ali normally used by a soluble salt of a hydroxy compound of the cyclic organic series. I

4. In a process of dyeing materials by a vatting method, the step of replacing, at least partially, the strong alkali normally used by a soluble salt of hydroxy compound of the homocyclic organic series.

6. In a process of dyin materials by a vatting method, the step 0 replacing, at least partially, the strong alkali normally used by a salt of a hydroxy compound of the homocyclic organic series and having a monovalent inorganic base.

6. In a process of dyeingmaterials by a vatting method, the step of replacing, at least partially, the strong alkali normally used by a sodium salt of a hydroxy compound of the homocylic organic series.

7. In a process of dyeing materials com: prising artificial fibres derived from cellulose, by a vatting method, the step of replacing, at least partially, the strong alkali normally used by a soluble salt of a hydroxy compound of the cyclic organic series. 4

8. In a process of dyeing materials comprising artificial fibres derived from cellulose, by a vatting method, the step of replacing, at least partially, the strong alkali normally used by a soluble salt of a hydroxy compound of the homocyclic organic series.

9. In a process of dying materials coniprising artificial, fibres derived from cellulose, by a vatting method, the step of replacing, at least partially, the strong alkali normally used by a salt of a hydroxy compound of the homocyclic organic series and having a monovalent inorganic base.

10. In a process of dyeing materials comprising artificial fibres derived from cellulose, by a vatting method, the step of replacing, at least partially, the strong alkali normally used by a sodium salt of a hydroxy compound of the homocyclic organic senes.

11. In aprocess of dyeing materials comprising artificial fibres derived from cellulose, by a vatting method, the step of replacing, at least partially, the strong alkali normally used by a soluble salt of a hydroxy compound of the benzene series.

12. In a process of dying materials comprising artificial fibres derived from cellulose, by a vatting method, the step of replacing, at least partially, the strong alkali normally used by sodium phenate.

13. In a process of dyeing materials comprising cellulose acetate by a vatting method, the step of replacing, at least partially, the strong alkali normally used by a soluble salt of a hydroxy compound of the cyclic organic I -series.

i 14. In a process of dyeing materials com- 105 prising cellulose acetate by a vatting method, the step of replacing, at least partially, the stron alkali normally used by a solublesalt of a ydroxy compound of the homocyclic organic series.

15. In a process of dyeing materials com prising cellulose acetate by a vatting method, the step of replacing, at least partially, the strong alkali normally used by. a. salt of a hydroxy compound of the homocyclic organic ieries and having a monovalent morganic ase.

16. In a process of dyeing materials comprising cellulose acetate by a vatting method, the step of replacin at least partially, the12l strong alkali normal y used by a. sodium salt of a hydr oxy compound of the homocyclic organicseries.

17 In a process of dyeing materials comprising cellulose acetate by a vatting method, 12: the step of replacing, at least partially, the strong alkali normally used by a soluble salt of a hydroxy compound of the benzene series.

18. In a process of dyeing materials comprising cellulose acetate by a vatting method, 13

the step of replacing, at least partially, the strong alkali normally used by sodium phenate.

19. In a process for dyeing materials comprising cellulose acetate and cellulosic fibre by a vatting method, the step of replacing, at least partially, the strong alkali normally used by a soluble salt of the hydroxy compound of the cyclic organic series.

20. In a process for dyeing materials comprising cellulose acetate and cellulosic fibre by a vatting method, the step of replacing, at least partially, the strong alkali normally used by by a soluble salt of a hydroxy compound of the homocyclic organic series.

21. In a process for dyeing materials comprising cellulose acetate and cellulosic fibre by a vatting method, the step of replacing, at least partially, the strong alkali normally used by a salt of a hydroxy compound of the homocyclic organic series and having a monovalent inorganic base.

22. In a process for dyeing materials c0mprising cellulose acetate and cellulosic fibre by a vatting method, the step of replacing, at least partially, the strong alkali normally used by a sodium salt of a hydroxy compound of the homocyclic organic series.

23. In a process for dyeing materials comprising cellulose acetate and cellulosic fibre by avattingmethod,the step of replacing, at least partially, the strong alkali normally used by a soluble salt of a hydroxy compound of the benzene series. 7

24. In a process for dyeing materials comprising cellulose acetate and cellulosic fibre by .a vatting method, the step of replacing, at least partially, the strong alkali normally used by sodium phenate.

25. In a process for dyeing materials comprising cellulose acetate and cotton by a vatting method, the step of replacing, at least partially, the strong alkali normally used by a soluble salt of a hydroxy compound of the cyclic organic series.

26. In a process for dyeing materials comprising cellulose acetate and cotton by a vatting method, the step of replacing, at least partially, the strong alkali normally used by a soluble salt of a hydroxy compound of the homocyclic organic series.

27. In a process for dyeing materials comprising cellulose acetate and cotton by a vatting method, the step of replacing, at least partially, the strong alkali normally used by a salt of a hydroxy compound of the homocyclic organic series and having a monovalent inorganic base.

28. In a process for dyeing materials comprising cellulose acetate and cotton by a vatting method, the step of replacing, at least partially, the strong alkalinormally used by a sodium salt of a hydroxy compound of the homocyclic organic series.

29. In a process for dyeing materials comprising cellulose acetate and cotton by a vatting method, the step of replacing, at least partially, the strong alkali normally used by a soluble salt of a hydroxy compound of the benzene series.

30. In a process for dyeing materials com prising cellulose acetate and cotton by a vatting method, the step of replacing, at least partially, the strong alkali normally used by sodium phenate. In testimony whereof I have hereunto subscribed my name.

I GEORGE HOLLAND ELLIS; 

